TWI300431B - Squarylium-metal chelate compounds and optical recording media - Google Patents

Description

1300431 (1) Technical Field of the Invention The present invention relates to a squaraine-metal splicing compound suitable for use as a recording material in an optical recording medium, and relates to the squaraine-metal cleavage compound Optical recording medium. [Prior Art] Recordable DVD media has been developed into a compact disk. The possibility of increasing the recording capacity of a DVD medium is to develop a recording material that minimizes the formation of a recording pit, and to introduce an image compression technique such as Moving Picture Group-2 (MPEG-2). And improving the method of shortening the wavelength of the semiconductor laser used to read the recording groove. The AlGalnP laser diode system with a wavelength of 670 nm is the only red semiconductor laser that has been developed and commercialized as a bar code reader and measuring instrument. With the development of optical discs with high recording densities, red semiconductor lasers have been introduced and are actually used in the optical recording industry. For a digital versatile disc (DVD) drive system, a laser source with a wavelength ranging from 645 nm to 675 nm is the standard source. Commercially available products are currently only replicable DVD-ROM drives having a wavelength source of about 65 nanometers. In this case, the spectrum recordable DVD media must have superior light resistance and storage stability, and the laser beam with a wavelength of 645 nm to 67 5 nm can be recorded by an optical pickup system. Copy the data. -6 - (2) 1300431 In order to achieve the aforementioned performance, it is necessary to develop a recording groove material during illumination. Optical recording media using various organic dyes have been developed. The cyanine compound can be listed as an example of a material for use in an optical recording medium having a recording and copying material by light sensing from 645 nm to 675 nm. However, the conventional squaraine compound is apparently damaged, and the data is unstable and stably recorded at a wavelength ranging from 645 nm to 675 nm. Highly reflective DVDs using Dye-containing recording layers: DVD + R and DVR-R media) are reflected at the interface of the dye film. In order to simultaneously produce satisfactory recording sensitivity and reflectance, the birefringence of the film needs to be controlled within an appropriate range, that is, for light having a wavelength within a range of ±5 nm in the recording-reproduction wavelength, the recorded refractive index η is It is from 1.5 to 3.0, and the extinction coefficient k is < 0.3. In order to satisfy the optical properties of the recording layer, the dye film can be used as a recording-replicating wavelength in DVD + R, DVD-R and CD- at the absorption edge of the optical long wavelength, as shown in FIG. According to this, however, the optical properties at the aforementioned laser wavelengths often change due to the wave-cut relationship with the absorption edge. As a possible solution to increase the light resistance of the recording layer, the E-clamping compound is an example of a high light-resistant dye. However, the recording layer of the dye alone has a low absorption coefficient and cannot produce the aforementioned birefringence. A wide variety of organic dyes are used in the recording layer for recording. The squaric acid wavelength of the body of the light and can not be a body (multiple, the dye is between the layer itself > • 02 to absorb the R media type technology is very dense 3 wax - gold contains this appropriate (3) Examples of optical recording media of 1300431 organic dyes are as follows: (1) Single-write, multiple-read (w〇rM) optical discs, such as (i) those using cyanine dyes (Japanese Patent Application (jP_A) No. 60 -89842 and serial number 6 1 -25 8 8 6 ); and those who use phthalocyanine dye (jp-A No. 63 -3 799 1 and serial number 63-3 9 8 8 8 ). (2) Rewritable disc (CEKRs) such as (i) a combination of cyanine dye and metal reflective layer (JP-Α No. 02- 1 3 65 6 and serial number 02- 1 68446); (ii) a combination of phthalocyanine dye and metal reflective layer (JP-A No. 05 - 1 3 9044 ); and (iii) A combination of azo-metal clamp dyes and metal reflective layers (JP-A No. 08-231886 and serial number 0 8-295 8 1 1 ) 〇 (3) Digitally versatile compact discs (DVD-Rs) with large capacity, such as (i) combined with cyanine dye and metal reflective layer (JP-A No. 1 0 -23 5 999, and Pi〇neer R&D vol. 6, Νο·2, 1 996 ) ; (ii) A combination of a methylimine dye and a metal reflective layer (JP-A No. 08-283263 and serial number 10- 2734 84 ) ; (iii) using an azo-metal compound compound and a metal reflective layer (JP-A No. 10-36693, No. 1 1 - 1 24 8 3, and serial number 200 1 -3 223 5 6 ); (iv) A combination of a styryl dye and a metal reflective layer (JP-A No. 1 Bu 1 443 1 3 and No. 11-165466); (v) A combination of a waxy dye and a metal reflective layer (JP-A 1 0-3 3 795 8 and No. 200 1 -23 23 5 ); and (vi) A combination of other dyes and metal reflective layers (JP-A No. 10-309871 and serial number 10-309872). (4) 1300431 SUMMARY OF THE INVENTION It is an object of the present invention to provide a squaraine-metal splicing compound which can be used as a recording material in an optical recording medium, which can be applied to a gfi recordable DVD disc system. Another object of the present invention Provided is an optical recording medium using a squaraine-metal compounding compound and having good recording properties, satisfactory light resistance, and superior storage stability . In particular, the present invention provides a squaraine-metal compound compound represented by the following structural formula (1): a ························· ····..· ^^ | (1) (c) m where lanthanide indicates a metal atom that can be coordinated; "a", "b", and "c" are represented by the following structural formula (2) a squaraine dye ligand, wherein ''a" is different from "b"; and "c" may be the same or different from "a" or "b"; and "m" means 0 or 1:

X

(2) wherein R! and R2 are the same or different and each represents one of an alkyl group, an aralkyl group, a aryl group and a heterocyclic group, each of which may be substituted; and X represents a aryl group which may be substituted a heterocyclic group which may be substituted and one of z3 = ch- wherein Z3 represents a heterocyclic group which may be substituted. -9- (5) 1300431

Furthermore, the present invention provides an optical recording medium comprising a substrate and a recording layer disposed on or above the surface layer of the substrate, wherein the recording layer comprises two or more different types of squaraine-metal compound compounds as Record material. The optical recording medium of the present invention uses a mixture of two or more of the squaraine-metal staking compounds having a specific structure of the present invention as a dye for use in a recording layer. Therefore, the optical recording medium has improved optical properties such as wavelength dependence, and can be used in a new generation of high-capacity optical disc systems using laser beams of wavelengths from 645 nm to 675 nm. Preferably, the optical recording medium additionally contains a wax-metal compound compound in the recording layer. Therefore, it has superior light resistance and storage stability. [Embodiment] Squaraine-Metal Clamping Compound The squarylium-metal chelating compound is represented by the following structural formula (1)

Wherein the lanthanide represents a metal atom that can be coordinated; "a", "b" and "c" each represent a squaraine dye ligand represented by the following structural formula (2), wherein "a" is different from "" b"; and "c" may be the same or different from "a" or "b"; and "m" means 0 or 1: -10- (2) (6) 1300431

Wherein R! and R2 are the same or different, and each of the tables #^#' aryl and ZfCH- in the heterocyclic group may each take a 7 i group. a cyclyl group, an arylalkyl group, each of which may be substituted; a day v 7 ^ group, a heterocyclic group, and a lyophilic group, wherein the substituted heterocyclic group substituent X is preferably one of the X groups and the aryl group, 苴What is broken? ^

:CH- (3) wherein R 3 and R 4 may be the same or different from each other and each represents a substituted substituent — wherein R and R 4 may form a ring with an adjacent carbon atom: a hydrogen atom or an alkyl group; In the aralkyl group and the aryl group, each of which may represent a halogen atom, a substituted alkyl group, a substituted aryl group, an aryl group which may be substituted by (4), a cyano group, and a (tetra) group. - and n is the whole age of 0 to 4, where + is applied, when η is 2, 3 or 4, the same or different 'and adjacent two R6 can be together with two adjacent carbon atoms Form a ring. In the structural formulae (2) and (3), the alkyl moiety in the alkyl group and the alkoxy group - 11 ^ (7) 1300431 is preferably one having a linear or branched alkane having 1 to 15 carbon atoms. It is preferably more than 8 carbon atoms or has 3 to 8 carbon cycloalkyl groups. The detailed examples are methyl, ethyl, propyl, isopropyl, butyrate, second butyl, tert-butyl, pentyl, isopentyl, b-, 2-methylbutyl, and pentylene. Base, hexyl, cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. The aralkyl group is preferably a aryl group having 7 to 19 carbon atoms, and more preferably having 7 to 15 carbon atoms. Specific examples thereof include a benzyl group, a phenylpropyl group, a naphthylmethyl group, and the like. The aryl group is preferably an aryl group having 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms. Specific examples thereof include a phenyl group, a naphthyl group, a chamomile ring group, and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine heterocyclic group. Examples include groups derived from a heterocyclic compound each having at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur selenium atom as a constituent. The atom of the ring. Preferably, the total number of atoms constituting the heterocyclic ring and including the sub-group is five to eight, and five or six more preferably the heterocyclic ring may be monocyclic or fused or include two or more (preferably, More preferably two to six) heterocyclic monocyclic chain polycyclic rings, such as a benzene ring, a naphthalene ring, or a carbocyclic fused fused to a heterocyclic ring, the heterocyclic ring including an aromatic heterocyclic ring and a lipid Family heterocycle. The specific examples of the heterocyclic ring are a pyridine ring, a pyridine ring, a spray D ring, a porphyrin ring, an isoquinoline ring, a sorghum ring, an oxazoline ring, a D-codolin ring group, and an atomic group thereof. Isobutylbutyl, cyclopentyl, and phenylethylene have a fluorenyl atom. The compound atom or the ruthenium di- or octacyclic ring and the carbocyclic heterocyclic ring, 'naphthyridin-12-(8) 1300431 lanthanide ring, oxime ring, 吼15 ring, microphone D ring, Triterpenoid, four π ring, thiophene ring, furan ring, thiazole ring, indazole ring, anthracene ring, isoindole ring, ring, benzimidazole ring, benzotriazole ring, benzothiazole Ring, benzophenanyl, etc. D ring, anthracene ring, indazole ring, pyrrolidine ring, piperidine ring, piperidine ring, oxime ring, thiomorphine ring, homopiperidine ring, high piperidine ring, Tetrahydrogen D ratio steep ring, Q hydroquinoline ring, tetrahydroisoquinoline ring, tetrahydrofuran ring, tetrahydro d-pyrene ring, dihydrobenzofuran ring, tetrahydrocarbazole ring, and the like. The heterocyclic ring in the group may be any heterocyclic ring in the aforementioned heterocyclic ring. The heterocyclic ring may preferably be, for example, a porphyrin ring, a thiazoline ring, a thiazine ring, a diamino D-quinoline ring, a quinoxaline ring, and any of the heterocyclic rings. The detailed examples of Z3 are β丨D-porphyrin-2-ylidene, benzo[e]-D-porphyrin-2-forkyl, 2-benzothiazolidinediyl, naphtho[2,i_d]thiazole-2 (3H)-peptidyl, naphtho[l,2-d]thiazole-2(1H)-hetero, 1,4-dihydroquinolin-4-ylidene, iota, 2-monohydroquinoline-2 -cross base, 2 5 3 -dihydro-1 Η -imidin D and [4,5 - d ] D-quinone nf porphyrin _ 2-hetero, 2-benzo selenoquinone sulfhydryl, and the like . In the formula (3), R3 and R4 may form a ring together with an adjacent carbon atom such as an alicyclic hydrocarbon ring or an aliphatic heterocyclic ring. The alicyclic hydrocarbon ring of the present invention may be a saturated or unsaturated alicyclic hydrocarbon ring having three to eight carbon atoms, such as a cyclopropyl ring, a ring, a ring, a ring, a ring, a ring. a ring of a courtyard, a cyclooctane ring, a cyclopentene ring, a 1,3-cyclopentadiene ring, a cyclohexene ring, a cyclohexadiene ring, or the like. The aliphatic heterocyclic ring may be a saturated or unsaturated aliphatic heterocyclic ring having three to eight atoms constituting the ring, and those having five or six constituent atoms are preferred. Examples thereof are a pyrazoline ring, a pyrazolidine ring, a piperidine ring, a porphyrin ring, a morpholin ring, a pyran ring, an imidazol ring, a thiazoline ring, a imi-13-1300431 Ο) oxazoline ring, An oxazoline ring, and the like. In the formula (3), the adjacent two "R6" may form a replaceable ring together with two adjacent carbon atoms. The ring system of the present invention is a ring containing two adjacent carbon atoms on the benzene ring. Examples of the ring include an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, and the like. Examples of the substituent which the alkyl group may have are a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, and the like. The examples and the alkyl moiety in the alkoxy group are the same as those described above. BL [the arylalkyl group, the aryl group, the alkoxy group, the heterocyclic ring, and the smog ring may additionally have one or more substituents. The group may be any conventional substituent such as a hydroxyl group, a carboxyl group, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a nitro group, a substituted or unsubstituted amine group, and the like. Examples of the alkyl moiety in the substituted or unsubstituted alkyl and alkoxy groups are as described above. The substituted amine group includes a monoalkyl substituted amino group and a dialkyl substituted group. Amino group. The alkyl group of the present invention may be as described above. The number of substituents to be substituted on each group is not particularly limited. , may be selected according to the purpose and may be one or more (preferably one to five). In the structural formula (1), the metal atom which can be coordinated is a metal atom which may have two or two ligands Preferably, the trivalent metal atom is better. The preferred examples of the metal atom are Ming, Zinc, Copper, Iron, Nickel, Complex, Ming, Manganese, Bismuth, Vanadium and Titanium. Among them, squaraine-aluminum clamp The compound has superior optical properties as an optical recording material. The squaraine compound represented by the structural formula (2) (hereinafter may be referred to as "combination-14-(10) 1300431 substance 2") may be given the international publication number WO 〇 2/ The preparation method of the compound is described in detail below, and the preparation method of the compound is described in detail below. The synthesis scheme of the compound 2 is represented by the following reaction formula: (1) Reaction formula (1-a)

(2) Reaction formula (1-b)

ο OH compound (III) 〇

OH % (IV)

X

R1 \ ΝΙΝ

(3) Reaction formula (lc) Compound (IV) + XH In the above reaction formula, Ri and R2 have the meanings as described herein; Y represents, for example, a hydrogen atom, a potassium atom, a sodium atom, or the like; It is a methyl group. The preparation of the compound (III) of the reaction formula (la) is illustrated in the following -15-(11) 1300431. The compound (111) can be obtained by the compound (1) and the compound (11) having a molar ratio of (5) to 2:2. It is prepared in a solvent and, if necessary, in the presence of a base of 1 to 2 moles of a base at a temperature of from room temperature to 4 ° C for 3 minutes to 15 hours. Examples of the base include inorganic bases such as potassium carbonate, sodium carbonate, potassium oxynitride or the like, and organic bases such as triethylamine, sodium methoxide, or the like. Examples of the solvent include methanol, ethanol and dimethyl. Kealamine. The preparation of the compound (IV) according to the reaction formula (1-b) is explained below. The compound (IV) can be prepared by reacting the compound (III) in a basic solvent or an acidic solvent at room temperature to 40 ° C for 30 minutes to 15 hours to prepare an alkaline solvent, an aqueous solution of potassium carbonate, an aqueous solution of sodium carbonate, An aqueous solution of potassium hydroxide, and the like. Examples of the acidic solvent are a solution of 50 vol/vol% hydrochloric acid in an aqueous solution of dimethyl hydrazine, a solution of 50 vol/vol% hydrochloric acid in an aqueous solution of dimethylformamide, and the like. The preparation of the compound (2) according to the reaction formula (1-c) is described below. The compound (2) can be used in the solvent by the compound (IV) and the XH of 5 to 2 times the molar number of the compound and optionally in the solvent. Prepared by reacting at a temperature of 80 ° C to 120 ° C for 1 to 15 hours in the presence of 5 to 2 moles of a base. Examples of the solvent are alcohol solvents having two to eight carbon atoms, such as ethylene-6-(12) 1300431 alcohol, propanol, isopropanol, butanol or octanol, or an alcohol solvent with benzene, toluene, xylene or a mixture of its kind. The amount of the alcohol in the mixture is preferably 50 vol/vol or more. The preparation of the squaraine-metal chelating compound [compound (1)] represented by the structural formula (1) is explained below. Reaction formula (1-d) a + b + m ( c) + compound (1) wherein a, b, c, m and lanthanide have the meanings as defined above; and n + means metal lanthanum from 1 to 3 The price. The compound (1) can be obtained by using the squaraine compound (a), the squaraine compound (b), the squaraine compound (c), and the metal ion (Mn+) in a solvent in the presence of acetic acid at room temperature to 120°. Prepared by reacting at a temperature of C for 1 to 15 hours. Examples of materials used for the metal ion Mn + are tris(acetonitrile)aluminum, tris(ethylethenylacetate)aluminum, aluminum isopropoxide, aluminum butoxide, aluminum ethoxide, aluminum chloride, copper chloride, Copper acetate, nickel acetate, and the like. Examples of the solvent are a halogen solvent such as chloroform, dichloromethane, or the like; an aromatic solvent such as toluene, xylene, or the like; an ether solvent such as tetrahydrofuran, methyl tert-butyl ether, or And an ester solvent such as ethyl acetate or the like. The details of the squaraine compound (2) represented by the structural formula (2) are as follows. In the following table, nPr represents n-propyl; iPi* represents isopropyl; nBu represents n-butyl; and Ph represents phenyl. -17- (13)1300431

-18- (14)1300431

-19- (15) 1300431

Squaraine compound. S-15 H3C CH3 〇' H9 jT^j Cl CH3 〇nPr S-16 H3c\/ch3 ?' H〇\ X^L ch3 〇" ch3 S-17 ch3 〇cf3 S-18 CH3 〇nPr In the squaraine-metal compound (i) represented by the structural formula (1), the squaraine compound (a) and the squaraine compound (b) each serving as a ligand for the metal ruthenium are mutually phased. different. The squaraine compound (c) may be the same as or different from the ruthenic acid compound (a) or (b). When the squaraine compound (c) is different from the squaraine compound (a) or (b), only a substituent is required between the two compounds, and at least one of R2 and X is different. Optical Recording Medium The optical recording medium of the present invention has a substrate and at least one recording layer disposed on the surface layer of the substrate or -20-(16) 1300431, and may further comprise one or more layers of other enamels as needed. ~ Light-carrying recording medium The recording layer includes two or more gastric to metal-clamping compounds of the present invention as a recording material. ^The recording layer in the light-receiving recording medium is preferably in the form of squaraine-metal clamp

Further, the X port (1) further includes a nail-metal compound compound as a material for the i-recording, the metal-carrying compound containing the metal and the formazan compound (4) represented by the following knot (@) .

In the formula (4), the 'ring Y system means a nitrogen-containing 5-member or 6-membered ring which may be substituted and may be condensed with another ring; the lanthanide group represents an atomic group constituting the ring oxime; Each represents a substituent. In the formula (4), the ring Y is a member having at least one nitrogen atom or a "member ring. The z system is an atomic group constituting the ring γ and is selected from carbon (C) and a hetero atom such as N, fluorene. Or 3. The ring γ may be substituted and may be condensed with another ring X. The other ring X may be any aromatic carbocyclic ring, aliphatic carbocyclic ring, aromatic heterocyclic ring and aliphatic heterocyclic ring. The ring X may contain 4 to 1 2 constituent atoms, preferably 5 to 10 constituent atoms. In the structural formula (4), the substituent Α represents an alkyl group, an aryl group, a decyl group, an arylcarbonyl group or an alkoxycarbonyl group, each of which may be substituted The substituent B is represented by a group or an aryl group, and each of them may be substituted. ^21 - (17) 1300431 The detailed examples of the ring Y are a thiazole ring, a benzothiazole ring, an imidazole ring, and a benzimidazole ring. , thiadiazole ring, carbazole ring, benzoxazole ring, triazole ring, pyrazole ring, Df diazole ring, pyridine ring, anthracene ring, pyrimidine ring, pyridinium ring, three-till ring, _ ─ ─ ─ ─ ring And the substituents to be substituted on the ring Y may be the same as the heterocyclic ring. The alkyl group, the alkyl moiety in the alkylcarbonyl group, and the alkyl moiety in the alkoxycarbonyl group each preferably have 1 to 15 The carbon atom is more preferably 1 to 8 carbon atoms. The alkyl group or the alkyl moiety may be a chain or a cyclic alkyl group (cycloalkyl group). Examples of the alkyl group are a linear alkyl group such as a methyl group or a Base, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl or n-decyl; branched alkyl, such as isobutyl, isopentyl, 2- Methyl butyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-ethylbutyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl , 5-methylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 2- Ethylhexyl, 3-ethylhexyl, isopropyl, t-butyl, 1-ethylpropyl, 1-methylbutyl, 1,2-dimethylpropyl, 1-methylheptyl, 1-ethylbutyl, 1,3-dimethylbutyl, l52-dimethylbutyl, 1-ethyl-2-methylpropyl, 1-methylhexyl, ethylethylheptyl, bupropylbutyl , 1-isopropyl-2-methylpropyl, 1-ethyl-2-methylbutyl, 1-ethyl-2-methylbutyl, 1-propyl-2-methylpropyl, 1-methylheptyl, ethyl ethyl , 1-propylpentyl, 1-isopropylpentyl, 1-bromopropyl-2-methylbutyl, 1-isopropyl-3-methylbutyl, 1-methyloctyl, B Heptylheptyl, 1-propylhexyl, 1-isobutyl-3-methylbutyl, neopentyl, tert-butyl-22-(18) 1300431, third hexyl, third pentyl or third Octyl; cycloalkyl, such as cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-tert-butylcyclohexyl, 4-(2-ethylhexyl)cyclohexyl, decyl, iso An alkyl group, an adamantyl group, or the like. The alkyl group may have one or more substituents such as a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, a cyano group, a substituted aryl group, or a substituted group. Heterocyclic group. The alkyl group may be substituted with another group via an atom such as an oxygen, sulfur or nitrogen atom. Examples of the alkyl group substituted with another group via an oxygen atom include methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, butoxyethyl, ethoxyethoxyethyl, phenoxy Base, methoxypropyl, ethoxypropyl, piperidinyl, morpholinyl and the like. Examples of the alkyl group substituted by another group via a sulfur atom include methylthioethyl, ethylthioethyl, ethylthiopropyl, phenylthioethyl and the like. Examples of the hospital group substituted with another group via a nitrogen atom include dimethylaminoethyl, diethylaminoethyl, diethylaminopropyl, and the like. The aryl moiety in the aryl group and the arylcarbonyl group each preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms. Examples of aryl or aryl moieties are phenyl, naphthyl, anthracenyl, fluorenyl, phenalenyl, phenanthranyl, 9,10 phenyl phenanthryl, fluorenyl and the like. By. The aryl group may have one or more substituents such as a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, a cyano group, a substituted aryl group or a substituted heterocyclic group. The aryl group can also be substituted with an alkyl group via an atom such as an oxygen, sulfur or nitrogen atom. -23-(19) 1300431 The alkylcarbonyl group may be a group containing a carbonyl group and a substituted or unsubstituted alkyl group bonded directly to a carbon atom of the carbonyl group. The alkyl examples herein are the same as those described above. The arylcarbonyl group may be a group containing a carbonyl group and a Μ Φ or unsubstituted aryl group bonded directly to a carbon atom of a carbonyl group. The aryl examples herein are the same as those described above.

The alkoxycarbonyl group may be a group containing an oxycarbonyl group and a substituted or unsubstituted alkyl group bonded directly to the oxygen atom of the oxycarbonyl group. Examples of the alkyl group herein are the same as those described above.

The metal in the wax-metal compound compound may be any metal that can coordinate the wax compound. Examples of the metal are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, chromium, antimony, molybdenum, omnibus, antimony, bismuth, palladium, and oxides and halides thereof. Class. Among them, iron, indium, nickel, copper, zinc and IG are superior to the formazan-metal compounding compound which constructs a satisfactory optical recording material. The metal may be partially replaced by, for example, chlorine. Details of the nail-metal compound compound are as follows. In the table below, ph is a phenyl group. -24- (20)1300431

Molybdenum metal clamp compound.. > Metal Fl Br-N-N(C2H5)2 N — VCI3 F-2 v}-vH ti-^3 Produce N~N Ph〇1 CF 0, Ni F-3 &quot ;ΊΓ" nh n-ch=ch—/~S ό Ni F-4 (CH3)2iy^ N V-NH N-CH=CH—f \ (CH3)2N I ό Co F-5 h3co N^~ V —NH N—/~\ K ^ \=/ h3c〇9 Cu -25- (21)1300431

Metallurgical compound metal; F-6 〇Xr<3 6 Ni F-7 Co F -8 〇XJ-〇°- Cu F -9 H3CO Cl th: J Valley Cl h3co 9 ύ Cu F -12 ΓΝ> -νη Ν-^/Λ /,〇〆Ni -26- (22) 1300431

The recording layer of the recording medium consists of two or more (two to six are preferred) different squaraine-metal splicing compounds (1) ° squaraine-metal splicing compound (1) The total content in the recording layer is preferably from 5% by weight to 10% by weight, and more preferably from 6% by weight to 8% by weight. The total content of the wax-metal compound compound (if any) in the recording layer is preferably from 5% by weight to 50% by weight, more preferably from 20% by weight to 40% by weight, and the recording layer in the optical recording medium preferably contains Two or more different -27-(23) 1300431 type squaraine-metal splicing compounds (1) and one or more types of ketone-metal chelating compounds (5). In this case, the weight ratio of the squaraine-metal compound compound (1) to the wax-metal compound compound (5) is preferably from 90:10 to 50:50, and from 80:20 to 60: 40 is better. When the recording layer contains such components in a weight ratio within the foregoing range, the nail-metal-clamping compound (5) can effectively produce high light resistance' and the recording layer can be easily produced to suit system specifications ( DVD media specification) and satisfactory reflectance and birefringence of recording sensitivity. The recording layer may additionally contain one or more dye materials in addition to the squaraine-metal compound compound and the wax-metal compound compound. Examples of the dye material are a cyanine dye, a phthalocyanine dye, a piperonyl/thiopentanyl dye, a chamomile iron dye, an azo dye, a dye of a metal such as a composite salt of Ni or Cr, naphthoquinone/quinone Dyes, phthalic acid dyes, anthranilamide dyes, triphenylmethane dyes, triallylmethane dyes, ammonium/diammonium dyes and nitroso compounds. If desired, the recording layer may additionally contain additional components such as binders and stabilizers. The thickness of the recording layer is preferably from 100 to 5,000 angstroms (10 nm to 500 nm), more preferably from 500 to 3,000 angstroms (50 nm to 300 nm) for better recording sensitivity and satisfactory Reflectance. The recording layer of the optical recording medium should have satisfactory optical properties. For satisfactory properties, the recording layer is preferably recorded and reproduced at a shorter wavelength (i.e., in the range of 645 nm to 675 nm). The wavelength has a large erbium absorption band and can be recorded and replicated when irradiated with light of -28-(24) 1300431 wavelength near the longer wavelength edge of the absorption band. In other words, the recording layer preferably has a large refractive index and a large extinction coefficient at a recording-replication wavelength in the range of 645 nm to 675 nm. In particular, the recording layer itself preferably has a refractive index η of 1.5 to 3.0 and a 0.02 to 0.3 extinction coefficient k for light of a recording-reproduction wavelength of ± 5 nm. A refractive index of 1.5 or higher produces a satisfactory optical change and a high recording modulation factor. A 3.0 or lower refractive index produces a lower wavelength dependence, thus reducing the error at the record-replication wavelength. 0.0 2 or a smaller extinction coefficient k results in high recording sensitivity. A 0.3 to a lower extinction coefficient k tends to result in a reflectance of 50% or higher. If the recording layer itself has a low extinction coefficient k at a longer wavelength (67 5 nm), the recording layer preferably additionally contains maximum optics in addition to the squaraine-metal compound compound and the methyl wax-metal compound compound. A dye that absorbs peaks at longer wavelengths (67 5 nm). Examples of the dyes are phthalocyanine dyes, tetramethyl cyanine dyes, azo dyes, and the like. The content of the dye for adjusting the extinction coefficient k in the recording layer is preferably from 5% by weight to 20% by weight. The recording material used in the present invention (a mixture of two or more kinds of squaraine-metal compounding compounds) Or a mixture of two or more squaraine-metal compounding compounds and at least one wax-metal compounding compound having a thermal decomposition temperature of preferably from 200 ° C to 350 ° C, and 25 (rc to 3 5) 0t: More preferably. The thermal decomposition temperature below 200 °C often leads to a decrease in the storage stability of the recording tank. The thermal decomposition temperature higher than 350 ° C may cause a decrease in recording sensitivity. The thermal decomposition temperature system used in the present invention is It is indicated that the thermal equilibrium turning point is used in the thermogravimetric analysis (-29-(25) 1300431 TG). The substrate in the optical recording medium can usually have a guide rail having a depth of 1000 to 2500 angstroms (100 nm to 250 nm). The gauge of the guide rail used in the DVD medium is preferably 〇·7 μm to μm. The rail width is preferably 0.18 μm to 〇.40 μm at a half spectral width. At a half spectral width of 0.18 μm or more, Easy to achieve the tracking error signal with sufficient intensity When the half-spectrum width is 〇. 4 〇 micrometers or less, the broadening of the recording portion in the width direction can be prevented. Next, the configuration of the optical recording medium of the present invention will be described. Fig. 2, 2, and 2C are each shown as a CD. A diagram of a possible thin layer configuration of an optical recording medium of the -R medium. Figs. 2, 2, and 2C show the substrate 1, the recording layer 2, the undercoat layer 3, the protective layer 4, the hard coat layer 5, and the metal reflective layer 6. Figures 3A, 3B and 3C each show another possible thin layer configuration as an optical recording medium for recordable DVD media. Figures 3A, 3B and 3C show substrate 1, recording layer 2, undercoat 3, protection Layer 4, hard coat layer 5, metal reflective layer 6, protective substrate 7 and adhesive layer 8. The optical recording medium of Figures 3B and 3C has an adhesive layer on the protective layer 4 of the configuration of Figures 2A and 2C. 8 and protecting the substrate 7. When an optical recording medium is used as the DVD medium, it basically comprises a first substrate and a second substrate, and is bonded by using a recording layer via an adhesive layer. The recording layer may have a reflective layer. Disposed on the substrate with an undercoat layer and/or a protective layer placed in between and the surface layer may have this Thin layer for better function. The most commonly used configuration is as illustrated in Figure 3B. -30- (26) 1300431 First substrate 1, recording layer (organic dye layer) 2, metal reflective layer 6 The arrangement of the protective layer 4, the adhesive layer 8 and the second substrate 7. The other constituent materials are described below. The material of the substrate used in the present invention can be arbitrarily selected from the materials used in the conventional recording medium substrate. Various materials. Examples of materials for the substrate are acrylic resins such as poly(methyl methacrylate); vinyl chloride resins such as poly(vinyl chloride) and vinyl chloride copolymers; epoxy resins; polycarbonates. Resin; amorphous polyolefin; polyester; glass, such as soda lime glass; and ceramic. Among them, poly(methyl methacrylate), polycarbonate resin, epoxy resin, amorphous polyolefin, polyester and glass are more favorable for obtaining satisfactory shape stability, transparency and planarity, wherein the guide rail When the pits are formed on the surface of the substrate, the polycarbonate is more advantageous for obtaining better moldability. The recording layer can be disposed on the substrate with an undercoat layer placed therebetween for better planarity, better adhesion, and prevention of damage to the recording layer. Examples of materials for the undercoat layer are poly(methyl methacrylate), acrylic acid-methacrylic acid copolymer, styrene-maleic anhydride copolymer, poly(vinyl alcohol), N-methylol propylene. Indoleamine, styrene-sulfonic acid copolymer, styrene-vinyl toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, poly(vinyl chloride), chlorinated polyolefin, polyester, polyimine , vinyl acetate-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate and other polymeric substances; decane coupling agents and other organic substances; and inorganic oxides such as si 〇2 and ai2o3, inorganic fluorides such as MgF2, other inorganic substances, and the like. The thickness of the primer-31 - (27) 1300431 layer is usually from 0.005 μm to 20 μm, preferably from 0.01 μm to 1 μm. The optical recording medium may additionally include a pregroove layer for forming a guide rail or a recess and a ridge for displaying a material such as an address signal on the substrate or undercoat layer. As the material of the front layer, a mixture of at least one monomer (or oligomer) selected from monoesters, diesters, triesters and tetraesters of acrylic acid and a photopolymerization initiator can be used. The optical recording medium may additionally include a reflective layer on the recording layer for use in higher signal-to-noise ratio (S/N ratio) and reflectance and higher recording sensitivity. The light-reflecting substance as the material of the reflective layer is a substance having a high reflectance with respect to the laser light. Examples of such materials are metals and semimetals such as Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Μη, R e , Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, A1, Ca, In, Si, Ge, Te, Pb, P o, Sn,

Si, Nd and their like. Among them, Au, A1 and Ag are preferred. These materials may each be used alone or in combination as a mixture or alloy. The reflective layer has a thickness of typically from 100 to 3000 angstroms (from 10 nanometers to 300 nanometers). The optical recording medium can include a protective layer on the recording layer or reflective layer to physically and chemically protect the record. Layers and other layers. It may also comprise another protective layer on the opposite side of the substrate from the recording layer to improve scratch resistance and moisture resistance. Examples of materials for the protective layer are SiO, S i 0 2, M g F 2, S η 0 2 and other inorganic substances, and thermoplastic resins, thermosetting resins, and ultraviolet curable resins. The protective layer may have a thickness of preferably -32-(28) 1300431 of 500 angstroms (50 nm) to 50 μm. A method of manufacturing the optical recording medium of the present invention will be described below. The optical recording medium can be produced, for example, by a method comprising the steps of: forming a main layer directly or in the middle by using a coating-film forming method on a substrate having at least one of grooves and pits on the surface. a recording layer comprising a squaraine-metal chelating compound of the formula (1); using a vacuum-film formation method, directly or in the middle of placing another layer on the recording layer to form a light-reflecting layer; and on the light-reflecting layer A protective layer is formed. In particular, the manufacturing method preferably includes the following methods (i) to (iii). (i) a recording layer forming method for forming a layer containing a groove and/or a pit on a surface of a substrate using a coating-film forming method, directly or in the middle to form another layer, which is mainly represented by the structural formula (1) a recording layer of a squaraine-metal splicing compound; (ii) a method of forming a light-reflecting layer, forming a light-reflecting layer on the recording layer by directly or in the middle of a vacuum-film formation method; and on the light-reflecting layer A protective layer is formed and (iii) a protective layer forming method is formed, and a protective layer is formed on the reflective layer. The recording layer forming method is formed according to the foregoing method, prior to the substrate having the grooves and/or the pits on the surface, using the coating-film forming method, directly or in the middle to form another layer to form the main inclusion structure (1). The δ-recording layer of the squaraine-metal chelating compound. § Sheep g, the squaraine-metal smear compound of the formula (1) is dissolved in a solvent to form a coating liquid, and the coating liquid is applied to a substrate to form the recording layer. -33- (29) 1300431 Examples of the solvent for coating a liquid are known organic solvents such as an alcohol, a cellosolve, a halogenated carbon, a ketone, an ether, and the like. The coating liquid is preferably applied by spin coating to easily control the film thickness. The film thickness in this method can be controlled by adjusting the concentration and viscosity of the coating liquid and the drying temperature of the solvent. The undercoat layer may be formed on the substrate before the application liquid for the recording layer is applied to the upper layer to increase the planarity of the surface of the substrate, increase the adhesion, and prevent the recording layer from being damaged. The undercoat layer can be formed, for example, by dissolving or dispersing a substance for the undercoat layer in a suitable solvent to form a coating liquid, and according to a coating method such as spin coating, dip coating, extrusion coating, or The coating liquid is formed by applying the coating liquid onto the surface of the substrate. Reflective layer forming method In the manufacturing method, the reflecting layer is formed on the recording layer by directly or in the middle of sandwiching another layer to form a film in a vacuum. In particular, the aforementioned reflective substrate is applied, for example, by vapor deposition, sputtering or ion plating to form a light-reflecting layer over the recording layer. Protective layer forming method According to this manufacturing method, a protective layer is formed on the light reflecting layer. The material for the protective layer and containing the aforementioned inorganic substance and/or resin is applied by coating or film formation in a vacuum to form a protective layer. The protective layer is preferably formed using an ultraviolet curable resin by spin coating the resin and applying -34-(30) 1300431 ultraviolet rays to cure the resin. As described above, the present invention can provide an optical recording medium which can record and copy data using laser light having a wavelength of from 645 nm to 675 nm, and which has satisfactory light resistance and storage stability. The invention is further illustrated in detail with reference to the following examples, which are not to be construed as limiting. Example 1 The squaraine compound S-1 (〇·98 g) and the squarylium compound s-2 (0.98 g) were used in ethyl acetate (8 ml), acetic acid (0.12 g) and tris(ethylethyl hydrazyl). Acetic acid) aluminum (〇·83 g) was treated at 60 ° C for 5 hours to give a mixture containing the following compound A and compound b. The MS ([M-H]· ) m/z system of Compound A was 1552, and the compound B was 1 620.

And Ph is represented by wherein Pr is a propyl phenyl-35 (31) 1300431 compound B:

Wherein Pr is a propyl group; and Bu is a butyl group. Example 2 A total of 15 g of a compound having a chromatographic ligand from a squaraine compound s dye ligand is mismatched with an aluminum of 5 5 mg of a S- 2 derived squaraine dye ligand using 10 g 2 , 2,3,3 - tetrafluoropropanol treatment. Formation It was found that Compound A and Compound B were formed. The MS of the compound A ([Μ-ΗΓ) m/z system B was 1 620. Example 3 A first substrate and a second substrate were prepared. These polycarbonate circles having a base of 120 mm and a thickness of 0.6 have a guide rail pattern having a depth of about 1,600 angstroms (160 nm) and a rail bottom width of 0.74 micrometers. And the Ph group indicates that the -1 derived squaraine is analyzed from a solution of the squaraine compound at room temperature to be 1 5 52, and the compounds each comprise a disk having a diameter of about 0.22 μm on the surface. And -36-(32) 1300431 contains the solution of the squaraine-metal compound compound prepared in Example 2 [refer to (S -1 ) / (S -2 )] in Table 7 at the ratio shown in Table 7 It was mixed with a wax-metal compound compound F-2 (refer to F-2 in Table 2) to produce a coating liquid. The coating liquid was applied to the first substrate by spin coating to form a recording layer having a thickness of about 1 000 angstroms (100 nm). The properties of the dye are shown in Table 7. Next, an Ag film having a thickness of about 1400 angstroms (140 nm) was formed by sputtering on the recording layer using Ar as a sputtering gas to form a reflective layer. An ultraviolet curable resin protective layer having a thickness of about 4 μm is formed on the reflective layer, and the second substrate is bonded thereto by using a hot melt adhesive to produce an optical recording medium (DVD + R medium) of Embodiment 3, which has The configuration of the first substrate, the recording layer (organic dye layer), the metal reflective layer, the protective layer, the adhesive layer, and the second substrate are sequentially arranged. The previously prepared optical recording medium was subjected to a reaction test, a light resistance test, and a storage stability test. The results are shown in Tables 7 and 8. The specularly reflective portion of the optical recording medium had a 68% reflectance at 64 5 nm and 86% at 675 nm. <Record test condition> The DVD (8-16) signal was recorded on the optical recording medium at a linear wavelength of 6.5 nm vibration wavelength, 开口65, and a linear velocity of 14 m/sec. The optimum laser power is 17 mW. The record recorded at 65 5 nm was reproduced using a DVD-R0M playback optical system having an aperture ratio NA of 〇·6〇 and a vibration wavelength of 650 nm, and the copy mode was measured. In addition, the groove edge-timer flutter is measured using a time interval analyzer. Light resistance test conditions Light resistance was measured by continuously irradiating the optical recording medium with Xe light at 50,000 lux for 30 hours, and then measuring the replica wave pattern. Storage stability test conditions Storage stability was measured by placing the optical recording medium at 50 ° C and 80% relative humidity RH for 600 hours, and then measuring the replica wave pattern. The optical recording medium of Example 3 had good results before and after the light resistance test and the storage stability test. Example 4 The optical recording medium (DVD + R medium) of Example 4 was prepared by the method of Example 3, and the solution containing the compound a and the compound B of the squaraine metal-clamping compound was shown in Table 7. The mixture is mixed with the wax-metal compound compound F-2 to produce a coating liquid. The squarylium metal chelating compound solution used herein was prepared by the method of Example 2, using a mixture of 1 gram of aluminum conjugate having a squaraine dye ligand derived from squaraine compound S-1. The compound is compounded with 60 g of an aluminum compound having a ligand of a squaraine dye derived from a squaraine compound S-2. The properties of the optical recording medium of Example 4 were determined by the method of Example 3 -38-(34) 1300431. The results are shown in Tables 7 and 8. The optical recording medium of Example 4 had good results before and after the light resistance test and the storage stability test. Example 5 The optical recording medium (DVD+R medium) of Example 5 was prepared by the method of Example 3, and the solutions of the squaraine-metal chelating compound containing the following compound C and the compound 不同 are listed in Table 7. The mixture is mixed with the wax-metal compound compound F-2 to produce a coating liquid. The squarylium metal chelating compound solution used herein was prepared by the method of Example 2, using 15 g of an aluminum compound having a squaraine dye ligand derived from a squaraine compound S-3. And 55 g of an aluminum-substituted compound having a squaraine dye ligand derived from the squaraine compound S-4. The properties of the optical recording medium of Example 5 were determined by the method of Example 3. The results are shown in Tables 7 and 8. The optical recording medium of Example 5 had good results before and after the light resistance test and the storage stability test. Compound C : -39- 1300431

Wherein Pr is a propyl group; Ph is a phenyl group; x is 1; and y is 2. Compound D:

Wherein Pr is a propyl group; Ph is a phenyl group; X is 2; and y is 1. Example 6 The optical recording medium (DVD + R medium) of Example 6 was prepared by the method of Example 3, and the solution of the squaraine-metal chelating compound containing the following compound E and compound F in different places is shown in Table 7. The mixture is mixed with the wax-metal compound compound F-2 at a ratio to produce a coating liquid. The squarylium metal chelating compound solution used herein is prepared by the method of Example 2-40-1300431. The use of 15 g of a ligand having a self-squaring sulphur compound S-6-derived squaraine dye is used. The aluminum compound is compounded with 55 g of an aluminum compound having a ligand of a squaraine dye derived from a stomach compound S-7. The properties of the optical recording medium of Example 6 were determined by the method of Example 3. The results are shown in Tables 7 and 8. The optical recording medium of Example 5 had good results before and after the light resistance test and the storage stability test. Compound E:

Wherein Pr is a propyl group; Bu is a butyl group; Ph is a phenyl group; X is 1; and y is 2. Compound F =

-41 - (37) 1300431 wherein pr represents propyl; Bu represents butyl; Ph is phenyl; X is 2; and y is 1. Comparative Example i The optical recording medium (DVD + R media) of Comparative Example 1 was prepared by the method of Μ 3, using an aluminum-substituted compound having a squarylium dye-derived ligand derived from squaraine compound 1 alone. (Compound G below) The properties of the optical recording medium of Comparative Example 1 were determined by the method of Example 3. The results are shown in Tables 7 and 8. Compound G:

Wherein Me represents a methyl group; Pr represents a propyl group; and Ph represents an example of the optical recording medium (DVD + R medium) of Comparative Example 1 by the method of Example 3, and the difference is by the mixing table 7 The ratio of the aluminum mis-synthesis mouth (the following compound G) having the squarylium dye-derived ligand derived from the squaraine compound S-1 is shown in the ratio of the methyl-metal-clamping compound F_2, to -42- (38) 1300431 Prepare the coating liquid. The properties of the optical recording medium of Comparative Example 2 were determined by the method of Example 3. The results are shown in Tables 7 and 8. Compound G:

Wherein Me represents a methyl group; Pr represents a propyl group; and Ph represents a phenyl group.

-43- 1300431 Original 値 动 (%) 丨 9 or lower 〇 od 〇〇 m od (N cK in a; modulation factor (%) 60 or higher 〇〇 § (N oo On 00 g reflectance (% 45 or higher m On (N in <N * Ϊ(Τ甲臜-Metal clamping compound 〇m Ph 〇of (3⁄4 F-2(30%) F-2(30%) 1 F-2( 30%) Thermal decomposition temperature (°C) (N 295 298 rH m 318 r^i oo CN vtv n/k (660 nm) 2.45/0.03 2.45/0.03 2.37/0.04 0.43/0.04 2.62/0.015 2.37/0.03 Acid Cyanine-Metal Clamp! i Compound S1/S-2 (70%) τ-Η GO S-3/S-5(70%) o 1 VO xjn o r1 Ή 00 o tH C/0 DVD+R Specifications Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2. Ugly _ Pine 4π^4πβι1ι collar-鼪. 向发<0^啪菝1|领-_氍枳长术砟1!} ^^||鼗*

-44- (40) 1300431 Table 8 Reflectance after modulation after light resistance test Reflectance factor reflectance factor (%) (%) (%) (%) DVD + R size 45 or higher 60 or higher 45 or more High 60 or higher Example 3 54 80 53 78 Example 4 49 80 49 80 Example 5 52 83 52 82 Example 6 52 82 5 1 79 Comparative Example 1 50 20 or lower Comparative Example 2 • BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the optical absorption spectrum and the recording-reproduction wavelength of a recording layer. 2A, 2B and 2C are each a schematic diagram showing the configuration of an optical recording medium used in the CD-R system of the embodiment of the present invention. 3A, 3B and 3C are each a schematic diagram showing the configuration of an optical recording medium used in the DVD + R system of the embodiment of the present invention. Description of component symbols: 1 : Substrate 2 : Recording layer 3 : Undercoat layer -45- (41) 1300431 4 : Protective layer 5 : Hard coat layer 6 : Metal reflective layer 7 : Protective substrate 8 : Adhesive layer - 46

Claims (1)

1300431 Patent application No. 93 1 03 3 75 Patent application Chinese patent application scope revision Amendment of May 14, 1997. 1. An optical recording medium comprising: a substrate; and at least one recording layer disposed thereon On or above the substrate, wherein the recording layer comprises two or more different squaraine-metal compound compounds represented by the following structural formula (1): wherein the lanthanide represents a metal atom capable of coordination; "," b and "c" each represent a squarylium dye ligand represented by the following structural formula (2), wherein 'a" is different; and "c" may be the same or different from "a" "or" b',; and "m" means 0 or 1: Wherein R! and R2 are the same or different and each represents one of an alkyl group, an aralkyl group, an aryl group and a heterocyclic group, each of which may be substituted; and X represents a aryl group which may be substituted, The substituted heterocyclic group and one of ZfCH-, wherein Z3 represents a heterocyclic group which may be substituted, 1300431, wherein the recording layer further comprises at least one methyl wax-metal compound compound, the compound comprising a metal and The formazan compound represented by the following structural formula (4): Vnh nb Wherein the Y ring system represents a 5- or 6-membered ring containing nitrogen, which may be substituted and condensed with another ring; Z-form represents an atomic group constituting the Y ring; and each of VIII and B represents a substituent. 2. An optical recording medium as claimed in claim 1, wherein the X system is represented by the following structural formula (3): R4 R3 Wherein R 3 and FU may be the same or different and each represents a substituted or unsubstituted substituent, wherein R 3 and R 4 may form a ring together with an adjacent carbon atom; Rs represents a hydrogen atom, a substituted alkyl group, One of a substituted aralkyl group and a substituted aryl group; R6 represents a halogen atom, a substituted alkyl group, a substituted aralkyl group, a substituted aryl group, a nitro group, a cyano group And one of alkoxy groups; and f'n" represents an integer from 〇 to 4, wherein when η is 2, 3 or 4, R0 may be the same or different from each other, and adjacent two "R6" The optical recording medium of claim 1, wherein M -2- 1300431 is a trivalent metal, the weight of which should be the same as .02 The optical recording medium of claim 3, wherein the trivalent metal is an inscription. 5. The optical recording medium of claim 1, wherein the recording layer comprises two to six Different types of squaraine-metal tongs. 6 · Optical recording as in claim 1 The optical recording medium of the squaraine-metal-clamping compound in the recording layer is from 50% by weight to 100% by weight. - the ratio of the amount of the metal-clamping compound to the formazan-metal-clamping compound is from 90:10 to 50:50. 8. The optical recording medium of claim 1, wherein the recording material has a temperature of 200 ° The thermal decomposition temperature of C to 350 ° C. 9. The optical recording medium of claim 1 wherein the recording layer has a thickness of from 100 angstroms to 5,000 angstroms (10 nm to 500 nm). The optical recording medium of claim 1 wherein the recording medium is recorded and reproduced by applying light having a wavelength of from 645 nm to 675 nm, and the recording layer itself is in a wavelength range of light for recording and reproduction. Within ±5 nm, having a refractive index n of 1.5 to 3.0 and an extinction coefficient k of 0 to 0.3. 11. The optical recording medium of claim 1 wherein the substrate of the -3-1300431 substrate has a groove At least one of a groove and a groove. 12. If the patent application scope The optical recording medium of claim 1, further comprising a reflective layer on or above the recording layer. 13. The optical recording medium of claim 12, further comprising a protective layer on or above the reflective layer 14. The optical recording medium of claim 1 is used in any of CD-R, DVD+R and DVD-R media. -4-